Azolylmethyl-fluorocyclopropyl derivatives

ABSTRACT

New azolylmethyl-fluorocyclopropyl derivatives of the formula ##STR1## in which R represents ##STR2## and addition products thereof which acids or metal salts are very effective for combating fungi. 
     New oxiranes of the formula ##STR3## in which R has the abovementioned meaning, are valuable intermediates for the preparation of compounds of the formula (I).

This application is a continuation of application Ser. No. 08/026,663,filed Mar. 4, 19932, now abandoned.

The present invention relates to new azolylmethyl-fluorocyclopropylderivatives, to a process for their preparation, and to their use asfungicides.

It has already been disclosed that certain azolylmethylcyclopropylderivatives have fungicidal properties (compare EP-OS (EuropeanPublished Specification) 0,297,345). For example,1-(4-chlorophenyl)-2-(1-fluoro-cyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-olcan be used for combating fungi. The action of this substance is good,but sometimes leaves something to be desired when used at lowapplication rates.

New azolylmethyl-fluorocyclopropyl derivatives of the formula ##STR4##in which p1 R represents ##STR5## and their acid addition salts andmetal salt complexes have now been found.

It has furthermore been found that azolylmethyl-fluorocyclopropylderivatives of the formula (I) and their acid addition salts and metalsalt complexes are obtained when oxiranes of the formula ##STR6## inwhich R has the abovementioned meaning are reacted with 1,2,4-triazole,of the formula ##STR7## if appropriate in the presence of anacid-binding agent and in the presence of a diluent, and, ifappropriate, an acid or a metal salt are subsequently added onto theresulting compounds of the formula (I).

Finally, it has been found that the new azolylmethylfluorocyclopropylderivatives of the formula (I) and their acid addition salts and metalsalt complexes have very good fungicidal properties.

The substances according to the invention contain an asymmetricallysubstituted carbon atom. They can therefore be obtained in the forms ofoptical isomers. The present invention relates to the individual isomersas well as to the mixtures thereof.

Surprisingly, the substances according to the invention have betterfungicidal properties than1-(4-chlorophenyl)-2-(1-fluoro-cyclopropyl)-3-(1,2,4-triazol-1-yl)propan-2-ol,which is the active substance of the most similar constitution, has beenpreviously known and has the same direction of action.

Preferred acid addition salts of substances according to the inventionare those which are formed by adding the following acids ontoazolylmethyl-fluorocyclopropyl derivatives of the formula (I):

Hydrohalic acids such as, for example, hydrochloric acid and hydrobromicacid, in particular hydrochloric acid, furthermore phosphoric acid,nitric acid, sulphuric acid, mono- and bifunctional carboxylic acids andhydroxycarboxylic acids such as, for example, acetic acid, maleic acid,succinic acid, fumaric acid, tartaric acid, citric acid, salicylic acid,sorbic acid and lactic acid, as well as sulphonic acids such as, forexample, p-toluenesulphonic acid, 1,5-naphthalenedisulphonic acid andcamphorsulphonic acid, saccharin and thiosaccharin.

Preferred metal salt complexes of substances according to the inventionare addition products of salts of metals belonging to main group II toIV and sub-group I and II as well as IV to VIII of the Periodic Systemof the Elements with azolylmethyl-fluorocylopropyl derivatives of theformula (I). Salts of copper, zinc, manganese, magnesium, tin, iron andof nickel are particularly preferred here. Suitable anions of thesesalts are those which are derived from those acids which lead tophysiologically acceptable addition products. Particularly preferredacids of this type are, in this context, the hydrohalle acids such as,for example, hydrochloric acid and hydrobromic acid, furthermorephosphoric acid, nitric acid and sulphuric acid.

If 2-( 2-chlorobenzyl )-2-(1-fluoro-cyclopropyl )-oxirane is used asstarting material and 1,2,4-triazole as reactant, the course of theprocess according to the invention can be illustrated by the followingequation: ##STR8##

The oxiranes of the formula (II) required as starting materials in theprocess according to the invention were hitherto unknown. They can beprepared by reacting benzyl ketones of the formula ##STR9## in which Rhas the abovementioned meaning either α) withdimethyloxosulphoniummethylide, of the formula ##STR10## or β) withdimethylsulphonium methylide, of the formula ##STR11## in the presenceof a diluent.

The benzyl ketones of the formula (IV) can be prepared by

a) reacting, in a first step benzyl chlorides of the formula

    R--CH.sub.2 Cl                                             (VII)

in which

R has the abovementioned meaning, with an excess of zinc powder in thepresence of a diluent such as, for example, ethylene glycol dimethylether, at temperatures between 50° C. and 150° C. under a protective gasatmosphere, removing the excess zinc powder, and then

b) in a second step, reacting the benzyl derivatives formed, of theformula

    R--CH.sub.2 ZnCl (VIII)

in which

R has the abovementioned meaning, with 1-fluoro-cyclopropane-carboxylicacid chloride of the formula ##STR12## in the presence of a palladiumcatalyst such as, for example, bis-(triphenyl-phosphine)-palladium(II)chloride, and in the presence of a diluent such as, for example,ethylene glycol dimethyl ether, at temperatures between 20° C. and 100°C.

The compounds of the formulae (VII) and (IX) are known or can beprepared by processes known in principle (compare EP-OS (EuropeanPublished Specification) 0,436,348 and EP-OS (European PublishedSpecification) 0,461,483).

Dimethyloxosulphoniummethylide of the formula (V), which is required asreactant for carrying out variant (α) of the process for the preparationof oxiranes of the formula (II), is known (compare J. Am. Chem. Soc. 87,1363-1364 (1965)). In the above reaction, it is processed in the freshlyprepared state, by preparing it in situ by reactingtrimethyloxosulphonium iodide with sodium hydride or sodium amide, inparticular with potassium tert.-butylate or sodium methylate, or byreacting trimethyloxosulphonium chloride with aqueous sodium hydroxidesolution, in each case in the presence of a diluent.

Dimethylsulphonium methylide of the formula (VI), which is furthermoresuitable as reactant for carrying out variant (β) of the process for thepreparation of oxiranes of the formula (II) is also known (cf.Heterocycles 8, 397 (1977)). In the above reaction, it is also employedin the freshly prepared state, by preparing it in situ, for example fromtrimethylsulphonium halide or trimethylsulphoniummethylsulphate, in thepresence of a strong base such as, for example, sodium hydride, sodiumamide, sodium methylate, potassium tert.-butylate or potassiumhydroxide, in the presence of a diluent such as tert.-butanol ordimethyl sulphoxide.

Suitable diluents for carrying out the above process for the preparationof oxiranes of the formula (II) are inert organic solvents. Thefollowing can preferably be used: alcohols such as tert.-butanol, etherssuch as tetrahydrofuran or dioxane, furthermore aliphatic and aromatichydrocarbons such as benzene, toluene or xylene, and strongly polarsolvents such as dimethyl sulphoxide.

When carrying out the above process for the preparation of oxiranes ofthe formula (II), the reaction temperatures can be varied within asubstantial range. In general, the process is carried out attemperatures between 0° C. and 100° C., preferably between 10° C. and60° C.

When carrying out the above process for the preparation of oxiranes ofthe formula (II), 1 to 3 moles of dimethyloxosulphonium methylide of theformula (V), or of dimethylsulphonium methylide of the formula (VI), aregenerally employed per mole of benzyl ketone of the formula (IV). Theoxiranes of the formula (II) are isolated by customary methods.

Suitable acid-binding agents for carrying out the process according tothe invention are all customary inorganic and organic bases. Thefollowing can preferably be used: alkali metal carbonates such as sodiumcarbonate and potassium carbonate, furthermore alkali metal hydroxidessuch as sodium hydroxide and potassium hydroxide, furthermore alkalimetal alcoholates such as sodium methylate, sodium ethylate, potassiummethylate and potassium ethylate as well as potassium tert.-butylate,and furthermore lower tertiary alkylamines, cycloalkylamines andaralkylamines such as, in particular, triethylamine.

Suitable diluents for carrying out the process according to theinvention are all customary inert organic solvents. The following canpreferably be used: nitriles Such as acetonitrile, furthermore aromatichydrocarbons, such as benzene, toluene and dichlorobenzene, moreoverformamides such as dimethylformamide, as well as strongly polar solventssuch as dimethyl sulphoxide and hexamethylphosphoric triamide.

When carrying out the process according to the invention, the reactiontemperatures can be varied within a substantial range. In general, theprocess is carried out at temperatures between 0° C. and 200° C.,preferably between 50° C. and 150° C.

When carrying out the process according to the invention, 1 to 4 molesof azole of the formula (III) and 1 to 2 moles of base are preferablyemployed per mole of oxirane of the formula (II). The end products areisolated in the customary manner.

The azolylmethyl-fluorocyclopropyl derivatives of the formula (I)according to the invention can be converted into acid addition salts ormetal salt complexes.

Suitable acids for the preparation of acid addition salts of thecompounds of the formula (I) are preferably those which have alreadybeen mentioned in connection with the description of the acid additionsalts according to the invention as being preferred acids.

The acid addition salts of the compounds of the formula (I) can beobtained in a simple manner by customary salt formation methods, forexample by dissolving a compound of the formula (I) in a suitable inertsolvent and adding the acid, for example hydrochloric acid, are isolatedin a known manner, for example by filtration, and, if appropriate,purified by washing with an inert organic solvent.

Suitable salts of metals for the preparation of metal salt complexes ofthe compounds of the formula (I) are preferably those which have alreadybeen mentioned in connection with the description of the metal saltcomplexes according to the invention as being preferred metal salts.

The metal salt complexes of the compounds of the formula (I) can beobtained in simple manner by customary processes, for example bydissolving the metal salt in alcohol, for example ethanol, and addingthe solution to compounds of the formula (I). Metal salt complexes canbe isolated in a known manner, for example by filtration, and, ifappropriate, purified by recrystallisation.

The active compounds according to the invention have a powerfulmicrobicidal action and can be employed as fungicides.

Fungicides in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above may be mentioned as examples, butnot by way of limitation:

Xanthomonas species, such as Xanthomonas oryzae;

Pseudomonas species, such as Pseudomonas lachrymans;

Erwinia species, such as Erwinia amylovora;

Pythium species, such as Pythium ultimum;

Phytophthora species, such as Phytophthora infestans;

Pseudoperonospora species, such as Pseudoperonospora humuli orPseudoperonospora cubensis;

Plasmopara species, such as Plasmopara viticola;

Peronospora species, such as Peronospora pisi or P. brassicae;

Erysiphe species, such as Erysiphe graminis;

Sphaerotheca species, such as Sphaerotheca fuliginea;

Podosphaera species, such as Podosphaera leucotricha;

Venturia species, such as Venturia inaequalis;

Pyrenophora species, such as Pyrenophora teres or P. graminea (conidiaform: Drechslera, syn: Helminthosporium);

Cochliobolus species, such as Cochliobolus sativus (conidia form:Drechslera, syn: Helminthosporium);

Uromyces species, such as Uromyces appendiculatus;

Puccinia species, such as Puccinia recondita;

Tilletia species, such as Tilletia caries;

Ustilago species, such as Ustilago nuda or Ustilago avenae;

Pellicularia species, such as Pellicularia sasakii;

Pyricularia species, such as Pyricularia oryzae;

Fusarium species, such as Fusariumculmorum;

Botrytis species, such as Botrytis cinerea;

Septoria species, such as Septoria nodorum;

Leptosphaeria species, such as Leptosphaeria nodorum;

Cercospora species, such as Cercospora canescens;

Alternaria species, such as Alternaria brassicae and

Pseudocercosporella species, such as Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compounds according to the invention are particularlysuitable for combating Pyricularia oryzae and Pellicularia sasakii onrice, and for combating cereal diseases such as Leptosphaeria nodorum,Cochliobolus sativus, Pyrenophora teres, Pseudocercosporellaherpotrichoides, Erysiphe and Fusariumspecies. Moreover, they have avery good action against Venturia, Sphaerotheca and Botrytis.

The substances according to the invention can be converted into thecustomary formulations, such as solutions, emulsions, suspensions,powders, foams, pastes, granules, aerosols, very fine capsules inpolymeric substances and in coating compositions for seed, as well asULV formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents and/or foam-forming agents. In the case of the use of water as anextender, organic solvents can, for example, also be used as auxiliarysolvents. As liquid solvents, there are suitable in the main: aromatics,such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water; by liquefied gaseous extenders orcarriers are meant liquids which are gaseous at ambient temperature andunder atmospheric pressure, for example aerosol propellants, such asbutane, propane, nitrogen and carbon dioxide; as solid carriers thereare suitable: for example ground natural minerals, such as kaolins,clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceousearth, and ground synthetic minerals, such as highly-disperse silica,alumina and silicates; as solid carriers for granules there aresuitable: for example crushed and fractionated natural rocks such ascalcite, marble, pumice, sepiolite and dolomite, as well as syntheticgranules of inorganic and organic meals, and granules of organicmaterial such as sawdust, coconut shells, maize cobs and tobacco stalks;as emulsifying and/or foam-forming agents there are suitable: forexample non-ionic and anionic emulsifiers, such as polyoxyethylene fattyacid esters, polyoxyethylene fatty alcohol ethers, for example alkylarylpolyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates aswell as albumen hydrolysis products; as dispersing agents there aresuitable: for example ligninsulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 per cent byweight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, as well as inmixtures with fertilisers and growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, emulsifiable concentrates, emulsions, foams, suspensions,wettable powders, pastes, soluble powders, dusts and granules. They areused in the customary manner, for example by watering, spraying,atomising, scattering, dusting, foaming, brushing on and the like. It isfurthermore possible to apply the active compounds by the ultra-lowvolume method or to inject the active compound formulation or the activecompound itself into the soil. The seeds of the plants can also betreated.

On use, the application rate of the substances according to theinvention can be raised within a substantial range, depending on thenature of the application method.

For example, in the treatment of parts of plants, the active compoundconcentrations in the use forms are, in general, between 1 and 0.0001%by weight, preferably between 0.5 and 0.001%. In the treatment of seed,amounts of active compound of 0.001 to 50 g per kilogram of seed,preferably 0.01 to 10 g, are generally required. For the treatment ofthe soil, active compound concentrations of 0.00001 to 0.1% by weight,preferably 0.0001 to 0.02% by weight, are required at the place ofaction.

The preparation and the use of the substances according to the inventioncan be seen from the examples which follow.

Preparation Examples

EXAMPLE 1 ##STR13##

A solution of 5.33 g (23.51 mmol) of2-(2-chlorobenzyl)-2-(1-fluorocyclopropyl)-oxirane in 15 ml ofdimethylformamide is added dropwise at 80° C. with stirring to a mixtureof 4.87 g (70.54 mmol) of 1,2,4-triazole and 0.53 g (4.70 mmol) ofpotassium tert.-butylate in 20 ml of dimethylformamide. When theaddition has ended, the reaction mixture is stirred for 6 hours at 80°C. The solvent is subsequently stripped off under reduced pressure, andthe residue which remains is taken up in ethyl acetate/water. Theaqueous phase is extracted three times using ethyl acetate, and thecombined organic extracts are washed once using water. After drying ofthe organic phase over sodium sulphate and concentration under reducedpressure, the residue is chromatographed on silica gel using the eluentethyl acetate:cyclohexane=1:2 to 1:1. After evaporation of the eluate,4.3 g (62% of theory) of1-(2-chlorophenyl)-2-(1-fluorocyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-olare obtained in the form of a solid substance of melting point 99 to103° C.

Preparation of the starting substance: ##STR14##

10.3 ml of 45% strength aqueous sodium hydroxide solution are addeddropwise at room temperature in the course of one hour to a mixture of3.33 g (25.86 mmol) of trimethylsulphoxonium chloride and 5.0 g (23.51mmol) of 2-chlorobenzyl 1-fluorocyclopropyl ketone in 30 ml of toluene.When the addition has ended, stirring is continued for one hour at roomtemperature. The reaction mixture is diluted with a small amount ofwater, and the organic phase is separated off. The aqueous phase isextracted three times using cyclohexane. The combined organic extractsare dried over sodium sulphate and concentrated under reduced pressure.The residue is used for the further reaction without additionalpurification. ##STR15##

A mixture of 32.7 g (0.5 mol) of zinc powder, 56.4 g (0.35 mol) of2-chlorobenzyl chloride and 375 ml of dry ethylene glycol dimethyl etheris refluxed for 2 hours under a nitrogen atmosphere. The reactionmixture is subsequently filtered under nitrogen. The filtrate is treatedwith 36.7 g (0.3 mol) of 1-fluorocyclopropanecarboxylic acid chlorideand 21 mg (0.01 mol %) of bis(triphenylphosphine)-palladium(II)chloride, and refluxed for 2 hours under a nitrogen atmosphere. Aftercooling to room temperature, the reaction mixture is filtered and thenconcentrated under reduced pressure. The residue is taken up in toluene,the mixture is extracted by shaking with dilute aqueous hydrochloricacid, the organic phase is dried, and the solvent is stripped off underreduced pressure. The residue which remains is subjected to a fractionaldistillation. 55.4 g of an oil which, according to gas chromatogram,consists of up to 90% of 2-chlorobenzyl 1-fluorocyclopropyl ketone, areobtained. Accordingly, the yield is calculated as 75% of theory.

reparation of the comparison substance of the formula ##STR16##

A solution of 3.3 g (15.7 mmol) of2-(4-chlorobenzyl)-2-(1-fluorocyclopropyl)-oxirane in 10 ml ofdimethylformamide is added dropwise at 80° C. with stirring to a mixtureof 3.3 g (47.1 mmol) of 1,2,4-triazole and 0.35 g (3.14 mmol) ofpotassium tert.-butylate in 20 ml of dimethylformamide. When theaddition has ended, the reaction mixture is stirred for 13 hours at 80°C. The solvent is subsequently stripped off under reduced pressure, andthe residue which remains is taken up in water. The aqueous phase isextracted four times using dichloromethane. The combined organic phasesare dried over sodium sulphate and then concentrated under reducedpressure. The residue which remains is chromatographed on silica gelusing the eluent cyclohexane: ethyl acetate=2:1. After evaporation ofthe eluate, 2.2 g (47% of theory) of1-(4-chlorophenyl)-2-(1-fluorocyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-olare obtained in the form of a solid.

¹ H NMR (200 MHz, CDCl₃):=δ0.0-0.8 (m, 4H); 3.0 (AB system, 2H); 4.01(s,1H, OH); ##STR17##

21 ml of 45% strength aqueous sodium hydroxide solution are addeddropwise in the course of one hour at room temperature to a mixture of2.2 g (17.1 mmol) of trimethylsulphoxonium chloride and 3.3 g (15.5mmol) of 4-chlorobenzyl 1-fluorocyclopropyl ketone in 20 ml of toluene.When the addition has ended, stirring is continued for 2 hours at 40° C.The phases are subsequently separated, and the aqueous phase isextracted three times using toluene. The combined organic phases arewashed once with water, dried over sodium sulphate and concentratedunder reduced pressure. The residue is used for further reaction withoutadditional purification.

In the use examples which follow, the compound of the formula mentionedbelow was employed as comparison substance. ##STR18##

(Disclosed in EP-OS (European Published Specification) 0,297,345)

Example A

Erysiphe test (barley)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are dusted with spores of Erysiphe graminisf.sp. hordei.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-1) according to the invention shows adegree of effectiveness of 100% at a concentration of 250 ppm in thespraying liquid.

Example B

Erysiphe test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are dusted with spores of Erysiphe graminisf.sp. tritici.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation. In this test,the compound (I-1) according to the invention shows a degree ofeffectiveness of 100% at a concentration of 250 ppm in the sprayingliquid, whereas the comparison substance shows a degree of effectivenessof 85%.

Example C

Erysiphe test (barley)/curative

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for curative activity, young plants are dusted with spores ofErysiphe graminis f.sp. hordei. 48 hours after the inoculation, theplants are sprayed with the preparation of active compound untildew-moist.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation. In this test,the compound (I-1) according to the invention shows a degree ofeffectiveness of 100% at a concentration of 250 ppm in the sprayingliquid.

Example D

Erysiphe test (wheat)/curative

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for curative activity, young plants are dusted with spores ofErysiphe graminis f.sp. tritici. 48 hours after the inoculation, theplants are sprayed with the preparation of active compound untildew-moist.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%, in order to promotethe development of powdery mildew pustules.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-1) according to the invention shows adegree of effectiveness of 100% at a concentration of 250 ppm in thespraying liquid.

Example E

Fusarium nivale (var. majus ) test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofFusarium nivale (var. majus).

The plants are placed in a greenhouse under transparent incubationcovers at a temperature of approx. 15° C. under relative atmospherichumidity of approx. 100%.

Evaluation is carried out 4 days after the inoculation.

In this test, the compound (I-1) according to the invention shows adegree of effectiveness of 100% at a concentration of 250 ppm in thespraying liquid, whereas the comparison substance shows a degree ofeffectiveness of 40%.

Example F

Pyrenophora teres test (barley)/curative

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for curative activity, young plants are sprayed with a conidiasuspension of Pyrenophora teres. The plants remain in an incubationcabin at 20° C. and 100% relative atmospheric humidity for 48 hours. Theplants are then sprayed with the preparation of active compound untildew-moist.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-1) according to the invention shows adegree of effectiveness of 100% at a concentration of 250 ppm in thespraying liquid.

Example G

Leptosphaeria nodorum test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a spore suspension ofLeptosphaeria nodorum. The plants remain in an incubation cabin at 20°C. and 100% relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 10 days after the inoculation.

In this test, the compound (I-1) according to the invention shows adegree of effectiveness of 100% at a concentration of 250 ppm in thespraying liquid.

Example H

Gibberella zeae test (barley)/protective syn. Fusarium graminearum

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofGibberella zeae. The plants are placed in a greenhouse under transparentincubation covers at a temperature of approx. 20° C. under relativeatmospheric humidity of approx. 100%.

Evaluation is carried out 4 days after the inoculation.

In this test, the compound (I-1) according to the invention shows adegree of effectiveness of 100% at a concentration of 250 ppm in thespraying liquid.

Example I

Sclerotinia test (dwarf beans)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, 2 small agar pieces covered in growth ofSclerotinia sclerotiorum are placed onto each leaf. The inoculatedplants are placed in a darkened, humid chamber at 20° C. The size oflesions on the leaves is evaluated 3 days after inoculation.

In this test, the compound (I-1) according to the invention shows adegree of effectiveness of 100% at an active compound concentration of100 ppm in the spraying liquid.

Example K

Sphaerotheca test (cucumber)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are dusted with conidia of the fungusSphaerotheca fuliginea.

The plants are then placed in a greenhouse at 23° to 24° C. and at arelative atmospheric humidity of about 75%.

Evaluation is carried out 10 days after the inoculation.

In this test, the compound (I-1) according to the invention shows adegree of effectiveness of 100% at an active compound concentration of 1ppm in the spraying liquid.

Example L

Pyricularia test (rice)/protective

Solvent: 12.5 parts by weight: acetone

Emulsifier: 0.3 parts by weight: alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier tothe desired concentration.

To test for protective activity, young rice plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous sporesuspension of Pyricularia oryzae. The plants are then placed in agreenhouse at 100% relative atmospheric humidity and 25° C.

Evaluation of the disease infestation is carried out 4 days after theinoculation.

In this test, the compound (I-1) according to the invention, used at aconcentration of 0,025% in the spraying liquid, shows a degree ofeffectiveness of 80%, whereas the comparison substance (A) does not showany activity.

Example M

Pyricularia test (rice)/systemic

Solvent: 12.5 parts by weight: acetone

Emulsifier: 0.3 parts by weight: alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier tothe desired concentration.

To test for systemic properties, standard soil in which young riceplants have been grown is watered with 40 ml of the preparation ofactive compound. 7 days after the treatment, the plants are inoculatedwith an aqueous spore suspension of Pyricularia oryzae. Thereafter, theplants remain in a greenhouse at a temperature of 25° C. and a relativeatmospheric humidity of 100% until they are evaluated.

Evaluation of the disease infestation is carried out 4 days after theinoculation.

In this test, the compound (I-1) according to the invention, at anapplication rate of 100 mg of active compound per 100 cm², shows adegree of effectiveness of 100%, whereas the comparison substance (A)shows a degree of activity of 50%.

Example N

Pyrenophora tares test (barley)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofPyrenophora tares.

The plants then remain in an incubation cabin at 20° C. and 100%relative atmospheric humidity for 48 hours.

The plants are placed in a greenhouse at a temperature of about 20° C.and a relative atmospheric humidity of about 80%.

Evaluation is carried out 7 days after the inoculation.

In this test, the compound (I-1) according to the invention shows adegree of activity of more than 80% at an active compound concentrationof 250 ppm in the spraying liquid, whereas the comparison substance (A)shows a degree of 25%.

Example O

Fusarium nivale (var. nivale) test/wheat/protective

To produce a suitable preparation of active compound, sprayable,commercially available active compound formulation is in each casediluted with water to the desired concentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dewmoist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofFusarium nivale vat. nivale.

The plants are placed in a greenhouse in translucent incubation chambersat a temperature of about 15° C. and a relative atomspheric humidity ofabout 100%.

Evaluation is carried out 4 days after the inoculation.

In this test, the compound (I-1) according to the invention shows adegree of activity of 90% at an active compound concentration of 250 ppmin the spraying liquid, whereas the comparison substance (A) shows adegree of activity of 30%.

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswithin the spirit and scope of the invention will suggest themselves tothose skilled in the art.

What is claimed is:
 1. An azolylmethyl-fluorocyclo-propyl derivative ofthe formula ##STR19## in which R represents a group of the formula##STR20## or an addition product thereof with an acid or metal salt. 2.A compound according to claim 1, wherein such compound is1-(2-chlorophenyl)-2-(1-fluorocyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-olof the formula ##STR21##
 3. A compound according to claim 1, whereinsuch compound is1-(2,4-dichlorophenyl)-2-(1-fluorocyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-olof the formula ##STR22##
 4. A compound according to claim 1, whereinsuch compound is1-(2-difluoromethoxy-phenyl)-2-(1-fluorocyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-olof the formula ##STR23##
 5. A fungicidal composition comprising afungicidally effective amount of a compound or addition productaccording to claim 1 and an inert diluent.
 6. A method of combatingfungi, which method comprises applying to such fungi or to their habitata fungicidally effective amount of a compound or addition productaccording to claim
 1. 7. A method according to claim 6, wherein suchcompoundis1-(2-chlorophenyl)-2-(1-fluorocyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol,1-(2,4-dichlorophenyl)-2-(1-fluorocyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol,1-(2-difluoromethoxy-phenyl)-2-(1-fluorocyclopropyl)-3-(1,2,4-triazol-1-yl)-propan-2-olor.